LAS Glass Refining with Tin Oxide at Moderate Temperatures

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Solution Overview

Problem

The existing methods for refining glass melts for glass-ceramic production are costly and inefficient due to the need for high-temperature refining units and high refining agent contents, which lead to increased energy consumption and the risk of component evaporation, while also resulting in a high number of bubbles in the glass and ceramic products.

Innovation Solution

A process for refining a lithium aluminum silicate (LAS) glass melt using tin oxide as a refining agent with a content of ≤0.4% by weight, optimizing the melting tank design to minimize residence time and average glass temperature, allowing for refining at temperatures below 1700°C without additional high-temperature units, thereby reducing bubble formation to <1 bubble/kg melt.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Manufacturing precision

If high-temperature refining units are used to refine glass melt, then bubble removal is improved, but energy consumption increases and production costs increase

Engineering Contradiction:
Improvebubble qualityVSAvoidenergy consumption
Core Design Contradiction:
Manufacturing precisionVSUse of energy by moving object

Solution Approach 1:

The patent changes the temperature parameter from conventional high temperatures (>1750°C) to moderate temperatures (1600-1720°C), and adjusts the refining agent content parameter to optimize the refining process. This parameter change resolves the contradiction by achieving effective bubble removal at lower temperatures, thus reducing energy consumption while maintaining manufacturing precision.

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The patent uses moderate amounts of refining agents (≤0.4% by weight of tin oxide, or combinations with antimony and/or arsenic oxides) that perform their refining function and are then consumed or removed, avoiding the need for expensive, complex high-temperature refining units while achieving the desired bubble quality.

Inventive Principle:
Principle #27Cheap short-living objects (Disposable)

2Speed

If high refining agent contents are used to increase bubble diameter and rise rate, then bubble removal is improved, but batch costs increase and evaporation problems occur

Engineering Contradiction:
Improvebubble rise rateVSAvoidrefining agent content
Core Design Contradiction:
SpeedVSQuantity of substance

Solution Approach 1:

The patent optimizes the refining agent content parameter to moderate levels (≤0.4% by weight for tin oxide alone, or up to 0.5% when combined with antimony and/or arsenic oxides), which is sufficient to generate gas bubbles that rise at an adequate rate without causing excessive batch costs or evaporation problems during hot forming.

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The patent combines multiple refining agents (tin oxide with antimony and/or arsenic oxides) in specific proportions to achieve the desired bubble rise rate, effectively using a composite approach that reduces the total refining agent content needed while maintaining the speed of bubble removal.

Inventive Principle:
Principle #26Copying

3Productivity

If high temperatures are used during refining, then bubble growth and rise is accelerated, but component evaporation from the glass melt increases

Engineering Contradiction:
Improverefining speedVSAvoidcomponent evaporation
Core Design Contradiction:
ProductivityVSLoss of substance

Solution Approach 1:

The patent changes the temperature parameter from conventional high temperatures (>1750°C) to moderate temperatures (1600-1720°C), which maintains adequate refining speed through the use of optimized refining agent combinations while significantly reducing component evaporation losses from the glass melt.

Inventive Principle:
Principle #35Parameter changes

4Manufacturing precision

If additional high-temperature refining units are installed, then bubble removal is improved, but investment costs and device complexity increase

Engineering Contradiction:
Improvebubble qualityVSAvoidrefining unit configuration
Core Design Contradiction:
Manufacturing precisionVSDevice complexity

Solution Approach 1:

The patent extracts the refining function from separate, complex high-temperature refining units and integrates it into the main melting tank through the use of moderate-temperature refining with optimized refining agent combinations, thereby simplifying the overall device configuration while maintaining manufacturing precision.

Inventive Principle:
Principle #2Taking out (Extraction)

Solution Approach 2:

The patent makes the main melting tank perform both melting and refining functions at moderate temperatures through the use of refining agents, eliminating the need for separate specialized refining units and reducing device complexity while achieving the desired bubble quality.

Inventive Principle:
Principle #6Universality (Multi-functionality)

Applied Scientific Principles

This section explains which scientific principles are used to turn an abstract innovation direction into a practical engineering solution.

Function Achieved in This Case

This approach achieves high bubble quality in green glass and glass ceramic products with moderate refining agent content, reducing production costs and energy consumption while maintaining low bubble counts, as demonstrated by tank tests and mathematical simulations.

Implementation Method 1

Due to their static buoyancy due to the difference in density between the gas bubbles and the glass melt, the gas bubbles naturally tend to rise in the melt and then escape into the open.

Methodology Applied
Scientific EffectBuoyancy: Archimedes' Principle (Buoyancy)

Implementation Method 2

The bubbles grow or shrink when the pressure inside the bubble is higher or lower than the equilibrium pressure of the dissolved gases.

Methodology Applied
Scientific EffectPressure difference: Pressure Gradient

Implementation Method 3

the dissolved gases spontaneously form new bubbles on so-called germs (walls, mini-bubbles), which usually leads to foam

Methodology Applied
Scientific EffectNucleation: Nucleation

Data Source

PatentEP1757564B1Process to refine a glassmelt
Publication Date: 2014.10.29 SCHOTT AG
  • EP1757564B1 patent drawingFigure 1~2
  • EP1757564B1 patent drawingFigure 3
  • EP1757564B1 patent drawingFigure 4A~4B

AI summary

According to the prior art, the production of green glass for a LAS glass-ceramic with sufficiently low bubble counts requires either high concentrations of polyvalent refining agents or tin oxide (&gt; 0.5 wt%) at high melting/refining temperatures &gt; 1600°C or very high refining temperatures (&gt; 1750°C) with moderate refining agents (&lt; 0.25 wt%). Both options entail a number of serious disadvantages for the manufacturing process, the environment, and/or economic viability. To avoid these disadvantages, the invention provides a method for refining a glass melt for a glass-ceramic green glass with the following steps and a correspondingly designed melting furnace: - Providing a glass mixture based on a lithium aluminum silicate (LAS) glass system with the sole addition of tin oxide as a refining agent at a concentration &lt; 0.4 wt.-% without arsenic and/or antimony oxide as refining agent, - Design of the melting furnace with regard to minimum residence time of the glass to be refined and mean glass temperature according to the formula: tminT,x=2+0.5⋅1700-Tmit+50⋅0.40-x⁢h for Tmit≤1700°C and x≤0.40%mit Tmit=mean glass temperature;x=refining agent content, tmin=minimum residence time, and - Melting of the batch and refining of the melt at temperatures &lt; 1700°C without additional special high-temperature refining units.